There is a plethora of references (both patents and literature articles) dealing with the formation of intermediate oxidation products, one of the most important being adipic acid. Adipic acid is used to produce Nylon 66 fibers and resins, polyesters, polyurethanes, and miscellaneous other compounds.
There are different processes of manufacturing adipic acid. The conventional process involves a first step of oxidizing cyclohexane with oxygen to a mixture of cyclohexanone and cyclohexanol (KA mixture), and then oxidation of the KA mixture with nitric acid to adipic acid. Other processes include, among others, the "Hydroperoxide Process," the "Boric Acid Process," and the "Direct Synthesis Process," which involves direct oxidation of cyclohexane to adipic acid with oxygen in the presence of solvents, catalysts, and promoters.
The Direct Synthesis Process has been given attention for a long time. However, to this date it has found little commercial success. One of the reasons is that although it looks very simple at first glance, it is extremely complex in reality. Due to this complexity, one can find strikingly conflicting results, comments, and views in different references.
It is important to note that most, if not all, studies on the Direct Synthesis Process have been conducted in a batch mode, literally or for all practical purposes.
There is a plethora of references dealing with oxidation of organic compounds to produce acids, such as, for example, adipic acid.
The following references, among the plethora of others, may be considered as representative of oxidation processes relative to the preparation of diacids.
U.S. Pat. No. 5,463,119 (Kollar) discloses a process for the oxidative preparation of C.sub.5 -C.sub.8 aliphatic dibasic acids by
(1) reacting, PA0 (2) removing the aliphatic dibasic acid; and PA0 (3) recycling intermediates, post oxidation components, and derivatives thereof remaining after removal of the aliphatic dibasic acid into the oxidation reaction.
(a) at least one saturated cycloaliphatic hydrocarbon having from 5 to 8 ring carbon atoms in the liquid phase and PA1 (b) an excess of oxygen gas or an oxygen-containing gas in the presence of PA1 (c) a solvent comprising an organic acid containing only primary and/or secondary hydrogen atoms and PA1 (d) at least about 0.002 mole per 1000 grams of reaction mixture of a polyvalent heavy metal catalyst; PA1 (1) reacting, at a cycloaliphatic hydrocarbon conversion level of between about 7% and about 30%, PA1 (2) isolating the C5-C8 aliphatic dibasic acid. PA1 (a) feeding a predetermined amount or rate of a gaseous oxidant and a predetermined amount or rate of hydrocarbon into the reaction zone, the reaction zone attaining a first pressure; PA1 (b) measuring the rate of pressure-drop during the reaction by conducting at least one step of PA1 (c) adjusting the rate of the pressure-drop within a desired range by regulating a parameter in the reaction zone selected from a group consisting of temperature, feed of gaseous oxidant, composition of gaseous oxidant, pressure, feed of hydrocarbon, feed of solvent, feed of catalyst, feed of promoter, and a combination thereof; PA1 (d) repeating steps (a) to (c); PA1 (e) continuing repeating steps (a) to (c). PA1 a reaction chamber; PA1 oxidant feeding means coimected to the reaction chamber for feeding predetermined amounts or rates of a gaseous oxidant into said reaction chamber; PA1 at least one of PA1 pressure monitoring means connected to the reaction chamber for measuring pressure inside the reaction chamber; PA1 interrupting means for stopping temporarily in predetermined intervals feeding of gases into the reaction chamber and exiting of gases from the reaction chamber; and PA1 a controller connected to the pressure monitoring means for obtaining pressure related information from said pressure monitoring means; the controller being programmed to calculate pressure drop rate during said predetermined intervals, the controller also being connected to the at least one temperature monitoring means, the oxidant feeding means, the hydrocarbon feeding means, the solvent feeding means, the catalyst feeding means, and the promoter feeding means; the controller being programmed to adjust at least one of said temperature monitoring means, oxidant feeding means, hydrocarbon feeding means, solvent feeding means, catalyst feeding means, and promoter feeding means, in a manner to maintain the pressure drop rate within a desired range.
U.S. Pat. No. 5,374,767 (Drinkard et al.) discloses formation of cyclohexyladipates in a staged reactor, e.g, a reactive distillation column. A mixture containing a major amount of benzene and a minor amount of cyclohexene is fed to the lower portion of the reaction zone and adipic acid is fed to the upper portion of the reaction zone, cyclohexyladipates arc formed and removed from the lower portion of the reaction zone and benzene is removed from the upper portion of the reaction zone. The reaction zone also contains an acid catalyst.
U.S. Pat. No. 5,321,157 (Kollar) discloses a process for the preparation of aliphatic dibasic acids through oxidation of corresponding saturated cycloaliphatic hydrocarbons by
(a) at least one saturated cycloaliphatic hydrocarbon having from 5 to 8 ring carbon atoms in the liquid phase and PA2 (b) an excess of oxygen gas or an oxygen containing gas mixture in the presence of PA2 (c) less than 1.5 moles of a solvent per mole of cycloaliphatic hydrocarbon (a), wherein said solvent comprises an organic acid containing only primary and/or secondary hydrogen atoms and PA2 (d) at least about 0.002 mole per 1000 grams of reaction mixture of a polyvalent heavy metal catalyst; and PA2 (i) allowing the gaseous oxidant to cause a reaction in a manner that the reaction zone attains a second pressure, lower than the first pressure, at least partially resulting from the reaction; PA2 (ii) allowing the gaseous oxidant to cause a reaction and measuring the pressure drop within a predetermined interval of time; PA2 temperature monitoring means for monitoring the temperature in said reaction chamber; PA2 hydrocarbon feeding means connected to the reaction chamber for feeding a predetermined amount or rate of a hydrocarbon into said reaction chamber; PA2 solvent feeding means connected to the reaction chamber for feeding a predetermined amount or rate of a solvent into said reaction chamber; PA2 catalyst feeding means connected to the reaction chamber for feeding a predetermined amount or rate of a catalyst into said reaction chamber: PA2 promoter feeding means connected to the reaction chamber for feeding a predetermined amount or rate of a promoter into said reaction chamber;
U.S. Pat. No. 5,221,800 (Park et al.) discloses a process for the manufacture of adipic acid is disclosed. In this process, cyclohexane is oxidized in an aliphatic monobasic acid solvent in the presence of a soluble cobalt salt wherein water is continuously or intermittently added to the reaction system after the initiation of oxidation of cyclohexane as indicated by a suitable means of detection, and wherein the reaction is conducted at a temperature of about 50.degree. C. to about 150.degree. C. at an oxygen partial pressure of about 50 to 420 pounds per square inch absolute.
U.S. Pat. No. 3,987,100 (Barnette et al.) describes a process of oxidizing cyclohexane to produce cyclohexanone and cyclohexanol, said process comprising contacting a stream of liquid cyclohexane with oxygen in each of at least three successive oxidation stages by introducing into each stage a mixture of gases comprising molecular oxygen and an inert gas.
U.S. Pat. No. 3,957,876 (Rapoport et al.) describes a process for the preparation of cyclohexyl hydroperoxide substantially free of other peroxides by oxidation of cyclohexane containing a cyclohexane soluble cobalt salt in a zoned oxidation process in which an oxygen containing gas is fed to each zone in the oxidation section in an amount in excess of that which will react under the conditions of that zone.
U.S. Pat. No. 3,932,513 (Russell) discloses the oxidation of cyclohexane with molecular oxygen in a series of reaction zones, with vaporization of cyclohexane from the last reactor effluent and parallel distribution of this cyclohexane vapor among the series of reaction zones.
U.S. Pat. No. 3,530,185 (Pugi) discloses a process for manufacturing precursors of adipic acid by oxidation with an oxygen-containing inert gas which process is conducted in at least three successive oxidation stages by passing a stream of liquid cyclohexane maintained at a temperature in the range of 140.degree. to 200.degree. C. and a pressure in the range of 50 to 350 p.s.i.g. through each successive oxidation stage and by introducing a mixture of gases containing oxygen in each oxidation stage in an amount such that substantially all of the oxygen introduced into each stage is consumed in that stage thereafter causing the residual inert gases to pass countercurrent into the stream of liquid during the passage of the stream through said stages.
U.S. Pat. No. 3,515,751 (Oberster et al.) discloses a process for the production of epsilon-hydroxycaproic acid in which cyclohexane is oxidized by liquid phase air oxidation in the presence of a catalytic amount of a lower aliphatic carboxylic acid and a catalytic amount of a peroxide under certain reaction conditions so that most of the oxidation products are found in a second, heavy liquid layer, and are directed to the production of epsilon-hydroxycaproic acid.
U.S. Pat. No. 3,361,806 (Lidov et al.) discloses a process for the production of adipic acid by the further oxidation of the products of oxidation of cyclohexane after separation of cyclohexane from the oxidation mixture, and more particularly to stage wise oxidation of the cyclohexane to give high yields of adipic acid precursors and also to provide a low enough concentration of oxygen in the vent gas so that the latter is not a combustible mixture.
U.S. Pat. No. 3,234,271 (Barker et al.) discloses a process for the production of adipic acid by the two-step oxidation of cyclohexane with oxygen. In a preferred embodiment, mixtures comprising cyclohexanone and cyclohexanol are oxidized. In another embodiment, the process involves the production of adipic acid from cyclohexane by oxidation thereof, separation of cyclohexane from the oxidation mixture and recycle thereof, and further oxidation of the other products of oxidation.
U.S. Pat. No. 3,231,608 (Kollar) discloses a process for the preparation of aliphatic dibasic acids from saturated cyclic hydrocarbons having from 4 to 8 cyclic carbon atoms per molecule in the presence of a solvent which comprises an aliphatic monobasic acid which contains only primary and secondary hydrogen atoms and a catalyst comprising a cobalt salt of an organic acid, and in which process the molar ratio of said solvent to said saturated cyclic hydrocarbon is between 1.5:1 and 7:1, and in which process the molar ratio of said catalyst to said saturated cyclic hydrocarbon is at least 5 millimoles per mole.
U.S. Pat. No. 3,161,603 (Leyshon et al.) discloses a process for recovering the copper-vanadium catalyst from the waste liquors obtained in the manufacture of adipic acid by the nitric acid oxidation of cyclohexanol and/or cyclohexanone.
U.S. Pat. No. 2,565,087 (Porter ct al.) discloses the oxidation of cycloaliphatic hydrocarbons in the liquid phase with a gas containing molecular oxygen and in the presence of about 10% water to produce two phases and avoid formation of esters.
U.S. Pat. No. 2,557,282 (Hamblet et al.) discloses production of adipic acid and related aliphatic dibasic acids; more particularly to the production of adipic acid by the direct oxidation of cyclohexane.
U.S. Pat. No. 2,439,513 (Hamblet et al.) discloses the production of adipic acid and related aliphatic dibasic acids and more particularly to the production of adipic acid by the oxidation of cyclohexane.
U.S. Pat. No. 2,223,494 (Loder et al.) discloses the oxidation of cyclic saturated hydrocarbons and more particularly to the production of cyclic alcohols and cyclic ketones by oxidation of cyclic saturated hydrocarbons with an oxygen-containing gas.
U.S. Pat. No. 2,223,493 (Loder et al.) discloses the production of aliphatic dibasic acids and more particularly to the production of aliphatic dibasic acids by oxidation of cyclic saturated hydrocarbons with an oxygen-containing gas.
German Patent DE 44 26 132 A1 (Kysela et al.) discloses a method for dehydration of process acetic acid from the liquid-phase oxidation of cyclohexane with air. in the presence of cobalt salt as a catalyst after separation of the adipic acid by filtration and the cyclohexane phase by phase separation, while simultaneously avoiding cobalt salt precipitates in the dehydration column, characterized in that the acetic acid phase to be returned to the beginning of the process is subjected to azeotropic distillation by the use of added cyclohexane, under distillative removal of the water down to a residual content of less than about 0.3 to 0.7 wt %.
PCT Demand International Publication WO 96/03365 (Costantini et al.) discloses a method of recycling a cobalt-containing catalyst in a reaction involving the direct oxidation of cyclohexane into adipic acid using an oxygen containing gas. The method is characterized in that the reaction mixture, obtained in a preceding stage where the cyclohexane was oxidized into adipic acid, of which at least part of the intermediate oxidation products, such as cyclohexanol and cyclohexanone, the carboxylic acid and water has been separated and of which at least part of the adipic acid formed has been recovered by crystallization, undergoes at least one extraction operation using at least one cosolvent or a mixture comprising a cosolvent and a carboxylic acid. The method is also characterized by the separation of a mixture containing at least part of the cobalt catalyst, part of the carboxylic acid and optionally residual quantities of other compounds and a solution containing the co-solvent and at least part of the glutaric and succinic acids formed during the oxidation reaction, and the carboxylic acid.
None of the above references, or any other references known to the inventors disclose, suggest or imply, singly or in combination, oxidation reactions to intermediate oxidation products under reaction rate controlled conditions subject to the intricate and critical controls and requirements of the instant invention as described and claimed.
Our U.S. Pat. Nos. 5,580,531, 5,558,842, 5,502,245, and our co-pending applications Ser. No. 08/477,195 (filed June 7, 1995), now U.S. Pat. No. 5,801,282, issued Sep. 1, 1998, Ser. No. 08/587,967 (filed Jan. 17, 1996), now U.S. Pat. No. 5,883,292, issued Mar. 16, 1999, and Ser. No. 08/620,974 (filed Mar. 25, 1996), now U.S. Pat. No. 5,654,475, issued Aug. 5, 1997, all of which are incorporated herein by reference, describe methods and apparatuses relative to controlling reactions in atomized liquids.
Our co-pending application, of Mark W. Dassel, Eustathios Vassiliou, David C. DeCoster, Ader M. Rostami, and Sharon M. Aldrich, titled "Methods and Devices for Controlling the Reaction Rate of a Hydrocarbon to an Acid by Making Phase-related Adjustments," filed on Mar. 6, 1997, and having a Ser. No. 08/812,847, is also incorporated herein by reference.
Our co-pending application, of Mark W. Dassel, David C. DeCoster, Ader M. Rostami, Sharon M. Aldrich, and Eustathios Vassiliou, titled "Methods and Devices for Preparing Dibasic Acids," filed on Mar. 27, 1997, and having a Ser. No. 08/824,992, now U.S. Pat. No. 5,922,908,issued Jul. 13, 1999; is also incorporated herein by reference.
All of the following patent applications, which were filed simultaneously with the present application are also incorporated herein by reference:
U.S. patent application Ser. No. 08/861,281 (now abandoned) of Mark W. Dassel, Eustathios Vassiliou, David C. DeCoster, Ader M. Rostami, and Sharon M. Aldrich, titled "Methods and Devices for Controlling the Reaction Rate of a Hydrocarbon to an Intermediate Oxidation Product by Monitoring Flow of Incoming and Outcoming Gases."
U.S. patent application Ser. No. 08/861,180 (now allowed) U.S. Pat. No. 6,103,933 of David C. DeCoster, Ader M. Rostami, Mark W. Dassel, and Eustathios Vassiliou, titled "Methods and Devices for Controlling the Oxidation Rate of a Hydrocarbon by Adjusting the Ratio of the Hydrocarbon to a Rate-Modulator."
U.S. patent application Ser. No. 08/861,176, now U.S. Pat. No. 5,824,868, issued Oct. 20, 1998, of Mark W. Dassel, Eustathios Vassiliou, David C. DeCostcr, and Ader M. Rostami, titled "Methods of Preparing an Intermediate Oxidation Product from a Hydrocarbon by Utilizing an Activated Initiator."
U.S. patent application Ser. No. 08/859,890, now U.S. Pat. No. 5,817,819, issued Oct. 6, 1998, of Ader M. Rostami, Mark W. Dassel, Eustathios Vassiliou, David C. DeCoster, titled "Methods and Devices for Controlling the Oxidation of a Hydrocarbon to an Acid by Regulating Temperature/Conversion Relationship in Multi-Stagc Arrangements."
U.S. patent application Ser. No. 08/861,210 (now abandoned) of Eustathios Vassiliou, Ader M. Rostami, David C. DeCoster, and Mark W. Dassel, titled "Pseudo-Plug-Flow Reactor."